Olefin block copolymers and production methods thereof

ABSTRACT

The present description relates to olefin block copolymers having excellent elasticity and processability in conjunction with enhanced heat resistance, and to a preparation method thereof. The olefin block copolymers comprise a plurality of blocks or segments that comprise ethylene or propylene repeating units and α-olefin repeating units at different mole fractions from one another, wherein the block copolymer shows peaks at the 2θ of 21.5±0.5° and 23.7±0.5° in a wide-angle x-ray diffraction (WAXD) pattern, and the peak ratio defined by (the peak area at 21.5±0.5°)/(the peak area at 23.7±0.5°) is no more than 3.0.

TECHNICAL FIELD

The present description relates to olefin block copolymers andproduction methods thereof.

BACKGROUND

A block copolymer refers to a copolymer consisting of a plurality ofblocks or segments of repeating units with different characteristicsfrom one another. It tends to be superior to typical random copolymersor polymer blends in its properties. For example, the block copolymermay comprise both of soft elastic blocks (referred to as “softsegments”) and hard crystalline blocks (referred to as “hard segments,”)and this makes it possible for the polymer to exhibit properties such asexcellent elasticity and heat resistance, together. More specifically,such block copolymers may have elasticity at a temperature equal to orhigher than the glass transition temperature of the soft segment and canhave relatively good heat resistance because they do not show athermoplastic behavior until they reach a temperature higher than theirmelting temperature.

Specific examples of the aforementioned block copolymer include triblockcopolymer of styrene and butadiene (SBS) and its hydrogenated product,which have been known to find applications in many fields due to theirsuperiority in heat resistance and elasticity.

Recently, olefin elastomers such as copolymers of α-olefins withethylene or propylene have been intensively studied for their use. Morespecifically, many attempts have been reviewed to employ such olefinelastomers in various fields, for example, in different uses forsubstituting for rubber materials. In a bid to make improvements on heatresistance of the olefin elastomers, some attempts have also been madeto adopt a block copolymer type elastomer in lieu of conventional randomcopolymer-based olefin elastomers (e.g., an ethylene-α-olefin randomcopolymer). Moreover, various approaches have come under review toprepare block copolymer type olefin elastomers with excellentprocessability through a simple process.

SUMMARY

The present description provides olefin block copolymers having enhancedheat resistance in conjunction with excellent elasticity andprocessability, and a production method thereof.

According to an embodiment of the present description is provided anolefin block copolymer comprising a plurality of blocks or segments thatcomprise ethylene or propylene repeating units and α-olefin repeatingunits at different mole fractions from one another,

wherein the block copolymer shows peaks at the 2θ of about 21.5±0.5° andabout 23.7±0.5° in a wide-angle x-ray diffraction (WAXD) pattern and thepeak area ratio as defined by (the peak area at about 21.5±0.5°)/(thepeak area at about 23.7±0.5°) is no more than about 3.0, for example,from about 1.2 to 3.0, or from about 1.5 to 2.7.

In the WAXD pattern of such olefin block copolymer, a full width at halfmaximum (FWHM) value of the peak shown at 21.5±0.5° can be at leastabout 0.45°, for example from about 0.45° to 0.60°, or from about 0.49°to 0.55°.

In addition, the olefin block copolymer may have a degree ofcrystallization from about 10 to 30% as calculated from the ratio of thecrystalline peak area to the pattern area in the WAXD pattern, and theblock copolymer may also have a crystallization temperature (T_(c)) of95 to 120° C. The olefin block copolymer may have a melting temperature(T_(m)) of about 110 to 135° C.

In its DSC pattern, the olefin block copolymer may also show a firstpeak at a melting temperature (T_(m)) of about 110 to 135° C., andoptionally a second peak at a temperature different from that of thefirst peak, for example at a temperature of 40 to 105° C., and the firstand the second peaks satisfy Mathematical Formula 1 as follows:

0≦A2/(A1+A2)<1  [Mathematical Formula 1]

in Mathematical Formula 1, A1 and A2 represent the areas of the firstand the second peaks, respectively.

Further, the olefin block copolymer comprises a plurality of blocks orsegments that comprise a hard segment comprising a first mole fractionof α-olefinic repeating units and a soft segment comprising a secondmole fraction of α-olefinic repeating units, with the second molefraction being higher than the first mole fraction. In this regard, themole fraction of the α-olefin repeating units contained in the entireblock copolymer can lie between the first mole fraction and the secondmole fraction.

Further, the olefin block copolymer may comprise 20-95 mol % of the hardsegments and 5-80 mol % of the soft segments, and the hard segments mayhave a higher value than the soft segments in terms of at least onecharacteristic among a degree of crystallization, a density, and amelting temperature.

The olefin block copolymer as described above may comprise about 80 to98 mol % of ethylene or propylene repeating units and a remaining amountof α-olefin repeating units, and may have a density of about 0.85 g/cm³to 0.92 g/cm³. In addition, the olefin block copolymer has a weightaverage molecular weight of about 5,000 to 3,000,000, and itspolydispersity index is between 2.5 and 6.

According to other embodiments of the present description is alsoprovided an olefin block copolymer comprising a plurality of blocks orsegments that comprise ethylene or propylene repeating units andα-olefin repeating units at different ratios from one another, whereinits DSC pattern shows a first peak at a melting temperature (T_(m)) of110 to 135° C., and optionally a second peak at a temperature differentfrom that of the first peak, for example at a temperature of 40 to 105°C., and the first and the second peaks satisfy Mathematical Formula 1 asfollows:

0≦A2/(A1+A2)<1  [Mathematical Formula 1]

in Mathematical Formula 1, A1 and A2 represent the areas of the firstand the second peaks, respectively.

According to another embodiments of the present description is alsoprovided a production method of olefin block copolymers. Such productionmethod comprises:

copolymerizing α-olefins with ethylene or propylene at a temperature of70 to 150° C. in the presence of a catalyst composition comprising ametallocene catalyst having a Group IV transition metal and a Lewis basefunctional group and a co-catalyst having a Lewis acid element and anorganic functional group, and there occur alternatively between themetallocene catalyst and the cocatalyst a first state wherein the Lewisbase functional group and the Lewis acid element form an acid-base bondand a second state wherein the metallocene catalyst and the cocatalysthas no interaction therebetween, and in the first state, the Group IVtransition metal of the metallocene catalyst and the organic functionalgroup of cocatalyst do interaction with each other.

In the production method, the α-olefin used as a monomer can be at leastone selected from the group consisting of 1-butene, 1-pentene,4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-undecene,1-dodecene, 1-tetradecene, 1-hexadecene, and 1-itocene.

Further, in the production method of the olefin block copolymer, themetallocene catalyst may comprise a metallocene compound of ChemicalFormula 1 and the cocatalyst may comprise a compound of Chemical Formula3:

In Chemical Formula 1, R1 to R17 are the same with or different fromeach other, and are independently hydrogen, a halogen, a C₁-C₂₀ alkylgroup, a C₂-C₂₀ alkenyl group, a C₆-C₂₀ aryl group, a C₇-C₂₀ alkylarylgroup, or a C₇-C₂₀ arylalkyl group, respectively, L is a straight orbranched chain C₁-C₁₀ alkylene group, D is —O—, —S— or —N(R)—, wherein Ris hydrogen, a halogen, a C₁-C₂₀ alkyl group, a C₂-C₂₀ alkenyl group, ora C₆-C₂₀ aryl group, A is hydrogen, a halogen, a C₁-C₂₀ alkyl group, aC₂-C₂₀ alkenyl group, a C₆-C₂₀ aryl group, a C₇-C₂₀ alkylaryl group, aC₇-C₂₀ arylalkyl group, a C₂-C₂₀ alkoxy alkyl group, a C₂-C₂₀heterocyclic alkyl group, or a C₅-C₂₀ heteroaryl group, and when the Dis —N(R)—, R can be linked with A to form a heterocycle comprisingnitrogen, for example, a five to eight membered heterocycle such aspiperidinyl or pyrrolydinyl moiety, M is a Group IV transition metal, X1and X2 are the same with or different from each other, and areindependently a halogen, a C₁-C₂₀ alkyl group, a C₂-C₂₀ alkenyl group, aC₆-C₂₀ aryl group, a nitro group, an amido group, a C₁-C₂₀ alkyl silylgroup, a C₁-C₂₀ alkoxy group, or a C₀-C₂₀ sulfonate group, respectively.

—[Al(R18)-O]_(n)—  [Chemical Formula 3]

In Chemical Formula 3, R18s are the same with or different from eachother, and are independently C1 to C20 hydrocarbon; or C1 to C20hydrocarbon substituted with a halogen; and n is an integer of at leasttwo.

In accordance with the present description, there can be provided olefinblock copolymers having enhanced heat resistance in conjunction withexcellent elasticity and processability, and a preparation methodthereof. In particular, such olefin block copolymers can be preparedthrough simple process steps with using a simplified catalyst system.

Accordingly, such olefin block copolymer can greatly contribute tocommercialization of the olefin elastomers that are superior in heatresistance and all the properties thereof and makes it possible for sucholefin elastomers to be properly substituted for rubber materials in arange of fields.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a view showing the WAXD pattern obtained from the experimentalexample as to the olefin block copolymers of the examples in comparisonwith a heat resistant olefin elastomer (the ethylene-α-olefinic blockcopolymer) and the ethylene-α-olefin random copolymer of the comparativeexamples.

DETAILED DESCRIPTION OF THE EMBODIMENTS

Hereinafter, the olefin block copolymer according to embodiments of thepresent description and the production method thereof will be explainedin further detail. However, these embodiments are presented as a mereillustration and the scope of the invention is not limited thereby.Moreover, it is apparent to a person of ordinary skill in the art thatthe embodiments may be modified in many ways.

In the entire specification, some terms are defined as follows unlessthey are particularly stated otherwise.

In the entire specification, the term “(olefin) block copolymer” refersto a copolymerized polymer of ethylene or propylene with α-olefins,wherein it comprises a plurality of repeating unit blocks or segmentsthat are distinguishable from one another as they differ in at least oneof their physical or chemical properties; for example, the content (molefraction) of the repeating units derived from ethylene (or propylene)and the α-olefins, respectively, a degree of crystallization, a density,or a melting temperature.

A plurality of such blocks or segments can comprise, for example,ethylene or propylene repeating units and α-olefin repeating units, butcomprise each of the repeating units at different contents (molefractions) from one another. By way of an example, a plurality of theblocks or the segments may comprise a hard segment of a hard crystallineblock comprising α-olefins at a first mole fraction and a soft segmentof a soft elastic block comprising α-olefins at a second mole fractionbeing higher than the first mole fraction. In this regard, the firstmole fraction can be lower than the mole fraction of the α-olefinrepeating units as measured for the entire block copolymer, while thesecond mole fraction may be higher than the mole fraction of theα-olefin repeating units as measured for the entire block copolymer.

In addition, a plurality of the blocks and the segments may bedistinguished from each other in terms of at least one of otherproperties such as a degree of crystallization, a density, and a meltingpoint. For example, in comparison with the soft segment of the softelastic block, the hard segment of the hard crystalline block may have ahigher value in terms of at least one or two characteristics of thedegree of crystallization, the density, and the melting temperature.

Besides the mole fractions of the ethylene or propylene repeating unitsand of α-olefin repeating units, the degree of crystallization, thedensity, and the melting temperature, the olefin block copolymers of theembodiment disclosed herein can also be defined by crystallinecharacteristics determined by a WAXD pattern or the like, which will beexplained below in further detail.

In such embodiment, the olefin block copolymer may comprise a pluralityof blocks or segments that comprise the ethylene or propylene repeatingunits and the α-olefin repeating units at different mole fractions fromone another. Further, such olefin block copolymer is characterized inthat its wide angle X-ray diffraction (WAXD) pattern shows peaks at the2θ of about 21.5±0.5° and about 23.7±0.5° and the peak area ratio asdefined by (the peak area at about 21.5±0.5°)/(the peak area at about23.7±0.5°) is no more than about 3.0.

In such embodiments, the olefin block copolymer is prepared fromcopolymerization of ethylene or propylene with an α-olefin, andcomprises repeating units derived therefrom, and the α-olefin repeatingunits derived from the α-olefin make it possible for the polymer to showexcellent elasticity.

In addition, because such olefin block copolymer is prepared by usingsuch a catalyst system as will be described herein below, it maycomprise a plurality of blocks or segments that comprise the ethylene orpropylene repeating units and the α-olefin repeating units at differentmole fraction from each other. For example, the block copolymer maycomprise the hard segments of the hard crystalline blocks comprising afirst mole fraction of the α-olefin repeating units and the softsegments of the soft elastic blocks comprising a second mole fraction ofthe α-olefin repeating units with the second mole fraction being higherthan the first mole fraction. At this time, the mole fraction of theα-olefin repeating units included in the entire block copolymer can havea value lying between the first mole fraction and the second molefraction. In other words, the first mole fraction can be lower than themole fraction of the α-olefin repeating units as calculated for theentire block copolymer, while the second mole fraction may be higherthan the mole fraction of the α-olefin repeating units as calculated forthe entire block copolymer.

As such, the olefin block copolymer of the embodiment comprises aplurality of blocks or segments. For example, because it includes a hardsegment of a hard crystalline block with a higher mole fraction of theethylene or propylene repeating units, the block copolymer according tothe embodiment may show a melting temperature as high as about 110 to135° C., about 115 to 130° C., or about 115 to 125° C. Such a meltingtemperature is higher than that of the previously known random copolymerof ethylene and α-olefins. Accordingly, the block copolymer of theembodiment may show enhanced heat resistance in comparison with thepreviously-known olefin elastomers such as a random copolymer ofethylene and an α-olefin, and it can also have an excellent level ofelasticity as an elastomer even at a higher temperature.

A plurality of the blocks or the segments being contained in the blockcopolymer of the embodiment, for example, the hard segments and the softsegments can be distinguished from each other by one or more of othercharacteristics such as a degree of crystallization, a density, or amelting temperature. For example, the hard segment of the hardcrystalline block comprising a higher mole fraction of the ethylene orpropylene repeating units may have a higher value in at least onecharacteristic of the degree of crystallization, the density, themelting point, and the like, in comparison with the soft segment of thesoft elastic block comprising a relatively higher mole fraction of theα-olefin. This may be due to the fact that the hard segments have ahigher degree of crystallization. Such blocks or segments can becharacterized and/or classified by a method of obtaining a (co)polymercorresponding to each block or segment and characterizing the same.

As such, the block copolymer of the embodiment comprises a plurality ofblocks or segments having different properties, and thus it can showexcellent heat resistance in conjunction with superb elasticity. Forexample, the block copolymer comprises the soft segment of the softelastic block, thereby showing excellent elasticity. Besides, since theblock copolymer comprises the hard segment of crystalline blocks havinga high melting point, it would not lose such excellent elasticity untilits temperature reaches the high melting temperature. Accordingly, theblock copolymer may exhibit excellent heat resistance.

Furthermore, the block copolymer of the foregoing embodiment may haveunique crystalline characteristics defined by a certain wide-angle X-raydiffraction (WAXD) pattern. These crystalline characteristics may bedetermined by the WAXD pattern wherein the peaks are shown at the 2θ ofabout 21.5±0.5° and about 23.7±0.5° and the peak area ratio defined by(the peak area at about 21.5±0.5°)/(the peak area at about 23.7±0.5°) isabout 3.0 or less, for example, about 1.2 to 3.0, or about 1.5 to 2.7.

In this regard, the area of each peak can be obtained by carrying outdeconvolution with respect to each peak shown in the WAXD pattern, andthe peak area ratio can be obtained therefrom. The drawing range of theWAXD pattern can be limited within the range of the 2θ from about 11° to35°. With the WAXD pattern being drawn to include each peak, one cancarry out deconvolution with a single line fitting by using theFundamental parameter (FP) approach of Bruker TOPAS program to obtainthe area of each peak and the ratio therebetween. In this regard, onecan use Chebychev 3rd order function as a background when operating theTOPAS program. In addition, regarding the peaks shown at the 2θ of about21.5±0.5° and about 23.7±0.5°, respectively, one can designate the 2θ ofabout 20 to 22° and about 22 to 24° as the center of each peak in theTOPAS program and carry out deconvolution with the single line fittingto obtain the area of each peak. The peak area ratio may be calculatedfrom the area of each peak thus obtained.

Moreover, what may be inferred from the presence of the aforementionedtwo peaks in the WAXD pattern is that there are orthorhombic (110) and(200) crystalline regions. In addition, since the peak area ratio is nomore than about 3.0, it may be expected that the abundance for each ofthe orthorhombic (110) and (200) crystalline regions would be within acertain range.

As such, the block copolymer of the embodiment is characterized in thatas determined by the WAXD pattern, it has certain crystallinecharacteristics such as the presence of the orthorhombic (100) and (200)crystalline regions and these crystalline regions exist at a certainratio therebetween. Such block copolymer may have a higher degree ofcrystallization than a random copolymer having a similar density, andsuch a high degree of crystallization can be indicated by acrystallization temperature (T_(c)) of the block copolymer. For example,the block copolymer has a crystallization temperature as high as about95 to 120° C., or about 100 to 115° C., or about 102 to 110° C.Therefore, the block copolymer of the embodiment is characterized by thehigh degree of crystallization as inferred from the aforementioned WAXDpattern, thereby exhibiting excellent heat resistance.

In addition, the block copolymer of the embodiment exhibits a highcrystallization temperature and unique crystalline characteristicsdefined by their WAXD pattern including the peaks at certain positionsand the peak area ratio therebetween. Accordingly, the block copolymerof the embodiment may undergo a more rapid crystallization after beingmelted in a melt process and thus enables a high speed molding.Therefore, the block copolymer of the embodiment can have excellentprocessability and moldability into a product. In particular, thecrystalline characteristics of the embodiment as defined by the positionof certain peaks and the ratio of the peak areas in the aforementionedWAXD pattern are novel ones of the block copolymer newly discovered inthe present description. The block copolymer of the embodiment havingsuch novel crystalline characteristics may undergo a more rapidcrystallization after being melted, and it can be processed more quicklyto have excellent moldability into a product, which will be proved bythe following examples.

In the WAXD pattern of the block copolymer of the embodiment, the fullwidth at half maximum (FWHM) value for the peak shown at about 21.5±0.5°may be about 0.45° or higher, for example, about 0.45° to 0.60°, orabout 0.49° to 0.55°. In this regard, the FWHM value for each peak canbe determined by using an area function of the Bruker EVA program. Byway of an example, in order to measure the FWHM value of the peak shownat about 21.5±0.5°, one may set the peak measuring range from about 20to 23° in the EVA program and use the function of such area to measurethe FWHM value of the corresponding peak.

The FWHM value of the block copolymer of the embodiment, which is atleast about 0.45°, may indicate that the peak shown at about 21.5±0.5°has a relatively broad shape and there are many orthorhombic (110)crystalline regions corresponding to the peak, the size of which arerelatively small. These results can also reflect unique crystallinecharacteristics of the olefin block copolymer of the embodiment. Theblock copolymer of this embodiment having such crystallinecharacteristics may show more enhanced processability and moldabilityinto a product in conjunction with excellent heat resistance. Incontrast with the block copolymer of this embodiment, theethylene-α-olefin block copolymer failing to meet the condition that theFWHM value is at least about 0.45° comprises many of relatively largecrystalline regions and thus exhibits different crystallinecharacteristics from the block copolymer of the embodiment. When beingcompared with the ethylene-α-olefin block copolymer having suchdifferent crystalline properties, the block copolymer of the embodimentcan have a higher crystallization temperature, excellent moldabilityinto a product, heat resistance, and the like.

In addition, the block copolymer of the foregoing embodiment may have adegree of crystallization from about 10 to 30%, or from about 15 to 25%,or from about 16 to 23% as calculated by the ratio of the crystallinepeak areas to the pattern area in the WAXD pattern. At this time,deconvolution is carried out for the peaks and the amorphous regionpatterns in the WAXD pattern to calculate the areas of each peak andamorphous region pattern, and then the degree of crystallization can becalculated according to Mathematical Formula 2 as follows. For example,each peak area and the pattern area of the amorphous regions can beobtained by conducting deconvolution with a single line fitting by usingthe Fundamental parameter (FP) approach of the Bruker TOPAS program. Inthis regard, specified methods for calculating each peak area are thesame as already explained in the above for the WAXD pattern, and thusdetailed explanations will be now omitted. In order to obtain thepattern area of the amorphous region, one may designate the 2θ of about11° to 35° as a range to be measured, and the center of the halo (theamorphous region pattern in the lower part of the crystalline peak)shown in this range as an approximate 2θ value around the middle of themeasuring range, and carry out deconvolution with single line fitting inthe same manner. On calculation of the degree of the crystallization,the drawing range of the WAXD pattern for calculating the pattern areaof the amorphous region and the area of each peak may be defined withinthe 2θ range of about 11° to 35°.

Degree of crystallization(%)={(B+C)/(A+B+C)}*100  [Mathematical Formula2]

In Mathematical Formula 2, A is, for example, the area of the WAXDpattern corresponding to the amorphous region in the 2θ range of about11° to 35°, for example, the area of the halo shown in the 2θ range ofabout 11° to 35°, and B is the area of the peak at about 21.5±0.5°, andC is the area of the peak at about 23.7±0.5°.

As such, the block copolymer of the embodiment has a degree ofcrystallization equal to or higher than a certain level, thus showing anincreased crystallization temperature such that the block copolymer mayundergo crystallization more quickly when being melted in a meltingprocess. For example, when the block copolymer is melted and molded intoa product with a temperature decreasing, the comparatively highcrystallization temperature and the relatively high degree ofcrystallization make it possible for the polymer to reach thecrystallization temperature more quickly, allowing a high speed moldingand processing into a product. Therefore, the block copolymer of theembodiment can have excellent processability and moldability into aproduct.

In addition, the unique crystallization characteristics of the blockcopolymer according to the embodiment can be confirmed by certaincharacteristics as shown in the DSC pattern. For example, such blockcopolymer has a first peak shown in the melting temperature range of 110to 135° C. and a second peak as optionally shown at a temperaturedifferent from that of the first peak, wherein the first peak and thesecond peak may satisfy Mathematical Formula 1 as follows:

0≦A2/(A1+A2)<1  [Mathematical Formula 1]

in Mathematical Formula 1, A1 and A2 represent the areas of the firstpeak and the second peak, respectively.

In this regard, one may determine the area of each peak in the DSCpattern by obtaining a DSC pattern for the block copolymer, setting abase line for each peak, and calculating the peak area over the baseline. In this regard, one may use a DSC measuring instrumentmanufactured by TA instrument Co. Ltd. In addition, one can designate asa base line the line connecting two points within the range of about±20° C. based on the top of each peak. For example, in the region wherethe curve on the DSC pattern has a second derivative below zero (0), onecan designate as a base line the line connecting two points having thelowest heat flow value within the range of about ±20° C. based on thetop of each peak. By contrast, in the region where the curve on the DSCpattern has a second derivative above zero (0), one can designate as abase line the line connecting two points having the highest heat flowvalue within the range of about ±20° C. based on the top of each peak.In the block copolymer of the embodiment, the first peak may appear inthe range of a melting temperature from about 110 to 135° C., or fromabout 115 to 130° C., and the second peak may not be shown separately,or may appear in the range from about 40 to 105° C. or from about 50 to90° C. with a lower strength or with a smaller area than that of thefirst peak. Therefore, in the temperature range wherein each peakappears, one can set the lowest value of the heat flow (for the regionwhere the second derivative is below zero) or the highest value of theheat flow (for the region where the second derivative is above zero) asthe apex of each peak, based on which the base line is determined and avalue for Mathematical Formula 1 may be obtained. In the block copolymerof the embodiment, the value for Mathematical Formula 1 is at leastabout zero and less than 1, and for example it can be from about zero to0.9, or from zero to 0.5, or about zero to 0.4, or about 0.05 to 0.38.

As such, the unique crystalline characteristics of the block copolymerof the embodiment can be confirmed by the fact that there appear(s) onepeak or optionally two peaks in the DSC pattern, and the ratio betweenthe peak areas is within a certain range. The block copolymer of theembodiment with such unique crystalline characteristics may have ahigher crystallization temperature in conjunction with excellent heatresistance and elasticity, and show enhanced moldability into a productwhen compared with the previously known olefin elastomers.

In the aforementioned embodiment, the olefin block copolymer maycomprise ethylene or propylene repeating units at a content (molefraction) of about 80 to 98 mol %, or about 80 to 93 mol %, or about 85to 95 mol %. In addition to the ethylene or propylene repeating units,the block copolymer may comprise α-olefin repeating units at a remainingcontent (mole fraction) of, for example, 2-20 mol % or about 7-20 mol %,or about 5-15 mol %. When the block copolymer of the embodimentcomprises such a mole fraction of the α-olefin repeating units, it canhave excellent elasticity, and its mole fraction of the ethylene orpropylene repeating units may be optimized, enabling the polymer to havea high melting point and excellent heat resistance.

Further, the block copolymer of the embodiment may comprise a hardsegment at a mole fraction of about 20 to 95 mol %, or about 25 to 90mol %, or about 20 to 85 mol %, and a soft segment at a remaining molefraction of, for example, 5 to 80 mol %, or about 10 to 75 mol %, orabout 15 to 80 mol %.

In this regard, the mole fraction of the hard segment can be calculatedby using Time Domain NMR(TD NMR) equipment. More specifically, the TDNMR equipment can be used to measure a Free Induction Decay (FID) for ablock copolymer sample and the FID may be obtained as a function of timeand intensity. In Mathematical Formula 3, one may change four constantsof A, B, T2_(fast), and T2_(slow) and derive a function having a graphmost similar to that of the FID function, through which the A, B,T2_(fast), and T2_(slow) of the sample may be determined. For reference,the hard segment have a rapid T2 (spin-spin relaxation time) relaxationderived therefrom and the soft segment a slow T2 (spin-spin relaxationtime) relaxation derived therefrom. Therefore, among the values of A, B,T2_(fast), and T2_(slow) determined in the above, the smaller T2 valuecan be determined as the T2 of the hard segment (i.e., T2_(fast)) whilethe larger T2 value can be determined as the T2 of the soft segment(i.e., T2_(slow))_(.) Through such procedure, one may calculate theconstants A and B together with the content (mol %) of the hard segment.

Intensity=A×EXP(−Time/T2_(fast))+B×EXP(−Time/T2_(slow))  [MathematicalFormula 3]

Determination of A, B, T2_(fast), T2_(slow) through the fitting

Hard segment(mol %)=A/(A+B)×100

In Mathematical Formula 3, the intensity and the time are the valuesderived from the results of the FID analysis, T2_(fast) is the T2(spin-spin relaxation time) relaxation for the hard segment, andT2_(slow) is the T2 (spin-spin relaxation time) relaxation for the softsegment. Further, A and B are the constants determined by the fittingand have the values proportionate to the content of each segment,representing the relative ratios of the hard segment and the softsegment, respectively.

As mentioned above, among a plurality of blocks or segments contained inthe block copolymer, the hard segment may refer to the hard crystallinesegment comprising a higher mole fraction of the ethylene or propylenerepeating units, and the soft segment may refer to the soft elasticsegment comprising a higher mole fraction of the α-olefin repeatingunits. When the block copolymer of the embodiment comprises the hardsegment and the soft segment at certain mole fractions, respectively, itmay have excellent elasticity due to the presence of the soft segmenttogether with a high melting temperature and enhanced heat resistancedue to the presence of the hard segment.

Further, the block copolymer of the embodiment may have a density ofabout 0.85 g/cm³ to 0.92 g/cm³, or about 0.86 g/cm³ to 0.90 g/cm³, orabout 0.86 g/cm³ to 0.91 g/cm³, and a weight average molecular weight ofabout 5,000 to 3,000,000, or about 10,000 to 1,000,000, or about 50,000to 200,000. In addition, the block copolymer has a molecular weightdistribution of about 2.5 to 6, or about 2.6 to 5 or about 2.5 to 3.5.As the block copolymer of the embodiment has such properties includingthe density, the molecular weight distribution, and the like, it mayhave characteristics suitable for an elastomer, excellent mechanicalproperties, processability, and the like. In particular, the blockcopolymer of the embodiment has a relatively high level of the molecularweight distribution of at least 2.5, showing excellent processability.

In addition, the block copolymer comprises α-olefin repeating unitstogether with the ethylene or propylene repeating units. Such α-olefinrepeating units can be any repeating unit derived from α-olefins such as1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene,1-decene, 1-undecene, 1-dodecene, 1-tetradecene, 1-hexadecene, or1-itocene. It can comprise the repeating units derived from at least twomonomers selected from the foregoing.

The block copolymer of the aforementioned embodiment may show excellentelasticity due to the inclusion of the α-olefin repeating units and itmay also have excellent heat resistance caused by well-defined blockscontained therein and a higher degree of crystallization. In addition,the block copolymer of the embodiment can show a higher crystallizationtemperature and novel crystalline characteristics determined by the WAXDpattern. Due to their crystalline characteristics, the block copolymerof the embodiment is able to achieve a more rapid crystallization whenbeing subjected to a melting process and thus its melting process wouldproceed faster and its processability or moldability into a product canbe enhanced. Therefore, the block copolymer of the embodiment willovercome the limitation on the field to which olefin elastomers areapplied and it will find application in a range of the fields requiringheat resistance.

The block copolymer of the embodiment may be adopted to substantiallyall the fields to which elastomers have been applied so far. Moreover,the block copolymer of the embodiment finds application in a variety offields to which prior-art elastomers have failed to be applied in effectdue to their low level of heat resistance such that rubber materialshave been used instead. For example, the block copolymer of theembodiment finds applications in uses for forming various productsincluding parts or interior materials for vehicles such as bumpers ortrim parts; packaging materials, different electrical insulationmaterials, and the like; diverse household items such as shoe soles,tooth brush grips, flooring materials, or device grips; all sorts ofadhesives such as a pressure-sensitive adhesive or a hot-meltingadhesive; hoses; and pipes. Of course, it can be applied for otherdifferent fields and uses.

In addition, not only may the block copolymer of the embodiment be usedalone but also it can be blended with other polymers, resins, or allsorts of additives to be used, and it can be used in any form such as afilm, a molded product, or a fiber.

Further, according to another embodiment of the present description isprovided a production method of the olefin block copolymer as describedabove. The production method of the olefin block copolymer may comprisesubjecting ethylene or propylene and an α-olefin to copolymerization atabout 70 to 150° C. in the presence of a catalyst composition whichcomprises a metallocene catalyst having a Group IV transition metal anda Lewis base functional group and a cocatalyst having a Lewis acidelement and an organic functional group. In particular, such productionmethod is characterized in that at the temperature of thecopolymerization, the metallocene catalyst and the cocatalyst arealternatively either in a first state wherein the Lewis base functionalgroup and the Lewis acid element make an acid-base bond or in a secondstate wherein no interaction occurs between the metallocene catalyst andthe cocatalyst. In the first state, the Group IV transition metal ofmetallocene catalyst and the organic functional group of the cocatalystmay also have interaction therebetween.

When the ethylene or propylene monomer and the α-olefin monomer aresubjected to copolymerization in the presence of the catalystcomposition comprising the cocatalyst and the metallocene catalyst withsuch characteristics, it is assumed that due to the followingtechnological reasons, the preparation of the block copolymer of theembodiment can be achieved.

The metallocene catalyst has the Group IV transition metal as the centermetal element while it comprises a Lewis base functional group having anunshared electron pair such as a functional group comprising oxygen,nitrogen, or sulfur. The cocatalyst being used together comprises aLewis acid element such as aluminum or boron capable of bonding with theunshared electron pairs and an organic functional group. When being usedin the polymerization system, these two types of the metallocenecatalyst and the cocatalyst may be in a first state wherein the Lewisbase functional group and Lewis acid element make a Lewis acid-base bondat the polymerization temperature while the Group IV transition metaland the organic functional group of the cocatalyst do interaction witheach other. Additionally, the catalyst and the cocatalyst may beoptionally in a second state wherein no interaction occurs between themetallocene catalyst and the cocatalyst, for example, the Lewis basefunctional group and the Lewis acid element fail to form a Lewisacid-base bond, or there occurs no interaction between the Group IVtransition metal and the organic functional group. In particular, thecatalyst and the cocatalyst may be alternatively either in the firststate or in the second state. This is because the energy gap between thefirst state and the second state is so small in the order of no morethan 10 kcal/mol, or no more than at least 5 kcal/mol that the catalystand the cocatalyst is expected to be capable of easily coming and goingover such energy threshold at the polymerization temperature.

Such energy gap may be easily determined by a person of ordinary skillin the art with using Gaussian program in a computational chemistrymanner. In this regard, the state wherein the Lewis acid-base bond ismade in the first state collectively refers to not only the case wherethe Lewis base functional group and the Lewis acid element are linkedtogether through a covalent bond or a coordination bond, but also thecase where they have interaction through a van der Waals force or asigmatropic bond corresponding thereto. In addition, the state whereinthe Group IV transition metal and the organic functional group of thecocatalyst have interaction may refer to the case where they make aninteraction with each other through the van der Waals force or thesigmatropic bond corresponding thereto. Moreover, the situation whereinno interaction occurs between the metallocene catalyst and thecocatalyst in the second state may refer to the case where no Lewisacid-base bond between the Lewis base functional group and the Lewisacid element is made for the catalyst and the cocatalyst, or the casewhere the Group IV transition metal and the organic functional grouphave no interaction therebetween.

In this regard, when the metallocene catalyst and the cocatalyst are inthe first state, the Lewis acid-base bond and the interaction betweenthe Group IV transition metal and the organic functional group have aneffect of allowing the space surrounding the central metal element ofthe metallocene catalyst to be narrowed. For this reason, in the firststate, the ethylene or propylene monomers may have an easier access tothe catalyst and be polymerized more readily than the relatively large,α-olefin monomer. By contrast, when the metallocene catalyst and thecocatalyst are in the second state, the space surrounding the centralmetal element of the metallocene catalyst becomes relatively broader sothat the large α-olefin monomer may have access to the catalyst moreeasily, and thus an increased content of the α-olefin monomers can bepolymerized.

As such, using the metallocene catalyst and the cocatalyst as specifiedin the above makes it possible to alternatively bring about the firststate causing a higher content of the ethylene or propylene monomers tobe polymerized and the second state causing a higher content of theα-olefin monomers to be polymerized. As a result, the olefin blockcopolymer obtained by the other embodiment may include hard segmentscomprising a higher mole fraction of the ethylene or propylene repeatingunits and soft segments comprising a higher mole fraction of theα-olefin repeating units. In particular, such olefin block copolymerscan be prepared by employing a more simplified catalyst system withoutusing a complicate catalyst system that includes two types of transitionmetal. As mentioned above, such olefin block copolymer may also comprisewell-defined blocks and exhibit novel crystalline characteristics.

In the production method of the other embodiments, the polymerizationtemperature may range from about 70° C. to 150° C., or from about 80° C.to 120° C., or from about 90° C. to 100° C. At such polymerizationtemperature, the energy threshold lying between the first and the secondstates may be easily overpassed, allowing the polymerization reactionfor each monomer to proceed efficiently. Therefore, at suchpolymerization temperature, it is possible to obtain more easily olefinblock copolymers having plenty of well-defined blocks and excellentcrystalline characteristics at high yields.

In addition, the production method of the other embodiment may adopt ametallocene catalyst which comprises a Group IV transition metal as thecentral metal element while including a Lewis base functional group, forexample a functional group having 0, N, or S with an unshared electronpair. The types of such metallocene catalyst are not particularlylimited, but taking into account the fact that such catalyst should beallowed to properly bring about the first state and the second state inan alternating manner, and also considering the polymerization activityfor the ethylene or propylene monomers and the α-olefin monomers in eachstate, one may use a metallocene compound represented by ChemicalFormula 1 for the metallocene catalyst:

In Chemical Formula 1, R1 to R17 are the same with or different fromeach other, and are independently hydrogen, a halogen, a C₁-C₂₀ alkylgroup, a C₂-C₂₀ alkenyl group, a C₆-C₂₀ aryl group, a C₇-C₂₀ alkylarylgroup, or a C₇-C₂₀ arylalkyl group, respectively, L is a straight orbranched chain C₁-C₁₀ alkylene group, D is —O—, —S— or —N(R)—, wherein Ris hydrogen, a halogen, a C₁-C₂₀ alkyl group, a C₂-C₂₀ alkenyl group, ora C₆-C₂₀ aryl group, A is hydrogen, a halogen, a C₁-C₂₀ alkyl group, aC₂-C₂₀ alkenyl group, a C₆-C₂₀ aryl group, a C₇-C₂₀ alkylaryl group, aC₇-C₂₀ arylalkyl group, a C₂-C₂₀ alkoxy alkyl group, a C₂-C₂₀heterocyclic alkyl group, or a C₅-C₂₀ heteroaryl group, and when the Dis —N(R)—, R can be linked with A to form a heterocycle comprisingnitrogen, for example, a five to eight membered heterocycle such aspiperidinyl or pyrrolydinyl moiety, M is a Group IV transition metal,and X1 and X2 are the same with or different from each other, and areindependently a halogen, a C₁-C₂₀ alkyl group, a C₂-C₂₀ alkenyl group, aC₆-C₂₀ aryl group, a nitro group, an amido group, a C₁-C₂₀ alkyl silylgroup, a C₁-C₂₀ alkoxy group, or a C₀-C₂₀ sulfonate group, respectively.

Such metallocene catalyst includes a Group IV transition metal (M) as acentral metal element while comprising an “A-D” functional group whereinA is linked to oxygen, sulfur, or nitrogen of the D having an unsharedelectron pair. Therefore, the unshared electron pair contained in thefunctional group “A-D-” may act as a Lewis base to form an acid-basebond with the Lewis acid element of the co-catalyst and the Group IVtransition metal may interact with the organic group of the co-catalyst.As a result, the metallocene catalyst and the cocatalyst may bealternatively either in the first state or in the second state, enablingthe copolymerization of the ethylene or propylene monomers and theα-olefin monomers.

Regarding the metallocene compound of Chemical Formula 1, a morespecific explanation as to each substituent will be given as follows:

The C₁-C₂₀ alkyl group includes a straight or branched chain alkylgroup, and its specific examples include, but are not limited to, amethyl group, an ethyl group, an propyl group, an isopropyl group, ann-butyl group, a tert-butyl group, a pentyl group, a hexyl group, aheptyl group, and an octyl group.

The C₂-C₂₀ alkenyl group includes a straight or branched chain alkenylgroup, and its specific examples include, but are not limited to, anallyl group, an ethenyl group, a propenyl group, a butenyl group, and apentenyl group.

The C₆-C₂₀ aryl group includes a monocyclic or a condensed cyclic arylgroup, and its specific examples include, but are not limited to, aphenyl group, a biphenyl group, a naphthyl group, a phenanthrenyl group,and a fluorenyl group.

The C₅-C₂₀ heteroaryl group includes a monocyclic or a condensed cyclicheteroaryl group, and its examples include, but are not limited to, acarbazolyl group, a pyridyl group, a quinolin group, a isoquinolingroup, a thiophenyl group, a furanyl group, a imidazolyl group, aoxazolyl group, a thiazolyl group, a triazine group, a tetrahydropyranylgroup, and tetrahydrofuranyl group.

Examples of C₁-C₂₀ alkoxy group include, but are not limited to, amethoxy group, an ethoxy group, a phenyloxy group, and a cyclohexyloxygroup.

Examples of the Group IV transition metal include, but are not limitedto, titanium, zirconium, and hafnium.

In light of a suitable activity and characteristics of the metallocenecompound of Chemical Formula 1, R1 to R17 in Chemical Formula 1 may alsobe independently hydrogen, a methyl group, an ethyl group, an propylgroup, an isopropyl group, an n-butyl group, a tert-butyl group, apentyl group, a hexyl group, a heptyl group, an octyl group, or a phenylgroup, respectively, and besides the foregoing, it can be anyone ofvarious substituents.

Further, in the metallocene compound of Chemical Formula 1, L is a C₄-C₈straight or branched chain alkylene group. In addition, the alkylenegroup may be unsubstituted or substituted with a C₁-C₂₀ alkyl group, aC₂-C₂₀ alkenyl group, or a C₆-C₂₀ aryl group.

In the metallocene compound, A of Chemical Formula 1 can be hydrogen, amethyl group, an ethyl group, an propyl group, an isopropyl group, ann-butyl group, a tert-butyl group, a methoxy methyl group, a tert-butoxymethyl group, an 1-ethoxy ethyl group, an 1-methyl-1-methoxy ethylgroup, a tetrahydropyranyl group, or a tetrahydrofuranyl group, and itcan be other various substituent groups, as well.

In addition, specific examples of the metallocene compound of ChemicalFormula 1 include, but are not limited to, a compound represented byChemical Formula 2:

In the production method of the other embodiment, the aforementionedmetallocene catalyst may be used together with a cocatalyst having aLewis acid element such as aluminum or boron and an organic functionalgroup. The types of the cocatalyst are not particularly limited, but fora representative example of such cocatalyst, mentions may be made of thecocatalyst compound represented by Chemical Formula 3 as follows:

—[Al(R18)-O]_(n)—  [Chemical Formula 3]

In Chemical Formula 3, R18s are the same with or different from eachother, and are independently a C1-C20 hydrocarbon; or a C1-C20hydrocarbon substituted with a halogen; and n is an integer of at leasttwo, for example, an integer of 2 to 6.

Such cocatalyst includes aluminum as a Lewis acid element and alsocomprises an organic functional group of R18. It can properly form aLewis acid-base bond together with the metallocene catalyst such as acompound of Chemical Formula 1, while interacting with the Group IVtransition metal of the metallocene catalyst. In addition, when themetallocene catalyst of Chemical Formula 1 being used, the energy gapbetween the first and the second states is not really large and thus atthe copolymerization temperature, the metallocene catalyst and thecocatalyst may be alternatively either in the first state or in thesecond state, enabling copolymerization of the ethylene or propylenemonomer and the α-olefin monomers to occur. In addition, the cocatalsytshows a proper polymerization activity for the ethylene or propylenemonomer and the α-olefin monomers when being used together with, forexample, the aforementioned metallocene catalyst of Chemical Formula 1.Accordingly, using the cocatalyst together with a suitable metallocenecatalyst enables one to prepare the olefin block copolymer of theembodiment more conveniently, which has a higher degree ofcrystallization along with well-defined blocks.

For examples of the cocatalyst of Chemical Formula 3, mentions may bemade of methyl aluminoxane, ethyl aluminoxane, isobutyl aluminoxane, andbutyl aluminoxane, among which methyl aluminoxane and the like can betypically used.

A catalyst composition comprising the metallocene catalyst and thecocatalyst may be prepared by a typical method such as bringing themetallocene catalyst into contact with the cocatalyst. In addition, if afurther cocatalyst is to be used, one may bring the metallocene catalystinto contact either with all the cocatalysts simultaneously or with eachof the cocatalysts one by one. At this time, it may be advantageous inlight of the interaction between the metallocene catalyst and thecocatalyst that the metallocene catalyst is brought into contact firstwith the cocatalyst of Chemical Formula 3 prior to being contacted withother cocatalyst.

In addition, the mole ratio between the metallocene catalyst and thecocatalyst is from about 1/5,000 to 1/2, or from about 1/1,000 to 1/10,or from about 1/500 to 1/20. With adopting such mole fraction, one mayhave the interaction between the metallocene catalyst and the cocatalystoccur properly while avoiding the problems caused by an excessive amountthe cocatalyst such as a decrease in the activity of the metallocene oran increase in the production cost.

In the preparation of the catalyst composition, an aliphatic hydrocarbonsolvent such as pentane, hexane, or heptane, or an aromatic hydrocarbonsolvent such as benzene or toluene may be used for a solvent. Moreover,the metallocene catalyst or the cocatalyst may be used as beingsupported on a carrier.

Further, the production method of the other embodiment comprises thestep of copolymerizing an ethylene or propylene monomer and an α-olefinmonomer in the presence of the catalyst composition including theforegoing metallocene catalyst and the cocatalyst. For the α-olefinmonomer, one may use at least one selected from the group consisting of1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene,1-decene, 1-undecene, 1-dodecene, 1-tetradecene, 1-hexadecene, and1-itocene.

In addition, the production method of the olefin block copolymeraccording to the other embodiment may be carried out under typicalconditions for preparing olefin copolymers except for the conditions setforth in the above. Specific examples for such copolymerizationconditions are described in the following examples.

EXAMPLES

Hereinafter, some examples will be given for better understanding of thepresent invention, but the following examples are presented only for amere illustration though, and the scope of the present invention shouldnot be construed to be defined thereby.

Production Example 1 1) Preparation of a Ligand Compound

In a THF solvent, a compound of tert-Bu-O—(CH₂)₆C1 and Mg(0) werereacted to provide 1.0 mole of a solution of a Grignard reagent,tert-Bu-O—(CH₂)₆MgCl. The Grignard reagent thus obtained was added to aflask containing 176.1 mL (1.5 mol) of MeSiCl₃ and 2.0 L of THF at −30°C., and the resulting mixture was stirred for at least 8 hours at roomtemperature and the solution filtered therefrom was dried under vacuumto provide tert-Bu-O—(CH₂)₆SiMeCl₂. (Yield: 92%)

To a reactor were added 3.33 g (20 mmol) of fluorene, 100 mL of hexane,and 1.2 mL (10 mmol) of methyl tert-butyl ether (MTBE) at −20° C., and 8ml of n-BuLi (2.5M in Hexane) was slowly added thereto, and stirred atroom temperature for six hours. After the completion of the stirring,the temperature of the reactor was down to −30° C. and at thistemperature, the fluorenyl lithium solution thus prepared was slowlyadded to a solution of 2.7 g (10 mmol) of tert-Bu—O—(CH₂)₆SiMeCl₂dissolved in 100 ml of hexane. The resulting mixture was stirred at roomtemperature for at least 8 hours, and then water was added thereto forextraction and the resulting product was subject to evaporation to give5.3 g of (tert-Bu-O—(CH₂)₆)MeSi(9-C₁₃H₁₀)₂. (Yield: 100%) The ligandstructure was determined by 1H-NMR.

1H NMR (500 MHz, CDCl₃): −0.35 (MeSi, 3H, s), 0.26 (Si—CH₂, 2H, m), 0.58(CH₂, 2H, m), 0.95 (CH₂, 4H, m), 1.17 (tert-BuO, 9H, s), 1.29 (CH₂, 2H,m), 3.21 (tert-BuO-CH₂, 2H, t), 4.10 (Flu-9H, 2H, s), 7.25 (Flu-H, 4H,m), 7.35 (Flu-H, 4H, m), 7.40 (Flu-H, 4H, m), 7.85 (Flu-H, 4H, d).

2) Preparation of the Metallocene Compound

To a solution prepared from 3.18 g (6 mmol) of(tert-Bu-O—(CH₂)₆)MeSi(9-C₁₃H₁₀)₂ and 20 mL of MTBE was slowly added 4.8ml of a n-BuLi solution (2.5M, in Hexane) at −20° C. Then, the mixturewas warmed to room temperature and reacted for at least 8 hours and thena slurry solution of the dilithium salt thus prepared was slowly addedat −20° C. to a slurry solution prepared from 2.26 g (6 mmol) ofZrCl₄(THF)₂ and 20 mL of hexane and further reacted at room temperaturefor eight hours. The precipitates were filtered and washed with hexaneseveral times to provide 4.3 g of (tert-Bu-O—(CH₂)₆)MeSi(9-C₁₃H₆)₂ZrCl₂in the form of a red solid. (Yield: 94.5%)

1H NMR (500 MHz, C6D6): 1.15 (tert-BuO, 9H, s), 1.26 (MeSi, 3H, s), 1.58(Si—CH2, 2H, m), 1.66 (CH2, 4H, m), 1.91 (CH2, 4H, m), 3.32(tert-BuO-CH2, 2H, t), 6.86 (Flu-H, 2H, t), 6.90 (Flu-H, 2H, t), 7.15(Flu-H, 4H, m), 7.60 (Flu-H, 4H, dd), 7.64 (Flu-H, 2H, d), 7.77 (Flu-H,2H, d)

Production Example 2 1) Preparation of a Ligand Compound

A ligand compound was prepared in the same manner as set forth inProduction Example 1 except for using tert-Bu-O—(CH₂)₄C1 instead oftert-Bu-O—(CH₂)₆C1 in the preparation of the ligand, and(tert-Bu-O—(CH₂)₄)MeSi(9-C₁₃H₁₀)₂ was obtained therefrom with a similaryield to that of Production Example 1. The ligand structure wasdetermined by 1H-NMR.

1H NMR (500 MHz, C6D6): −0.40 (MeSi, 3H, s), 0.30 (CH₂, 2H, m), 0.71(CH₂, 2H, m), 1.05 (tert-BuO, 9H, s), 1.20 (CH₂, 2H, m), 2.94(tert-BuO-CH₂, 2H, t), 4.10 (Flu-9H, 2H, s), 7.16 (Flu-H, 4H, m), 7.35(Flu-H, 4H, m), 7.35 (Flu-H, 2H, d), 7.43 (Flu-H, 2H, d), 7.77 (Flu-H,4H, d).

2) Preparation of the Metallocene Compound

(Tert-Bu-O—(CH₂)₄)MeSi(9-C₁₃H₉)₂ZrCl₂ was obtained in the same manner asset forth in Production Example 1 with a similar yield except for using(tert-Bu-O—(CH₂)₄)MeSi(9-C₁₃H₁₀)₂ instead of(tert-Bu-O—(CH₂)₆)MeSi(9-C₁₃H₁₀)₂.

1H NMR (500 MHz, C6D6): 1.14 (tert-BuO, 9H, s), 1.26 (MeSi, 3H, s), 1.90(CH2, 2H, m), 1.99 (CH2, 2H, m), 2.05 (CH2, 2H, m), 3.39 (tert-BuO-CH2,2H, t), 6.84 (Flu-H, 2H, m), 6.90 (Flu-H, 2H, m), 7.15 (Flu-H, 4H, m),7.60 (Flu-H, 6H, d), 7.80 (Flu-H, 2H, d)

Production Example 3 1) Preparation of a Ligand Compound

A ligand compound was prepared in the same manner as set forth inProduction Example 1 except for using tert-Bu-O—(CH₂)₈C1 instead oftert-Bu-O—(CH₂)₆C1 in the preparation of the ligand, and then(tert-Bu-O—(CH₂)₈)MeSi(9-C₁₃H₁₀)₂ was obtained therefrom with a similaryield to that of Production Example 1. The ligand structure wasdetermined by 1H-NMR.

1H NMR (500 MHz, C6D6): −0.40 (MeSi, 3H, s), 0.29 (CH₂, 2H, m), 0.58(CH2, 2H, m), 0.83 (CH₂, 2H, m), 0.95 (CH₂, 2H, m), 1.05 (CH₂, 2H, m),1.14 (tert-BuO, 9H, s), 1.30 (CH₂, 2H, m), 1.64 (CH₂, 2H, m), 3.27(tert-BuO-CH2, 2H, t), 4.13 (Flu-9H, 2H, s), 7.17 (Flu-H, 4H, m), 7.26(Flu-H, 4H, m), 7.37 (Flu-H, 2H, d), 7.43 (Flu-H, 2H, d), 7.78 (Flu-H,4H, d).

2) Preparation of a Metallocene Compound

(Tert-Bu-O—(CH₂)₈)MeSi(9-C₁₃H₉)₂ZrCl₂ was obtained in the same manner asset forth in Production Example 1 with a similar yield except for using(tert-Bu-O—(CH₂)₈)MeSi(9-C₁₃H₁₀)₂ instead of(tert-Bu-O—(CH₂)₆)MeSi(9-C₁₃H₁₀)₂.

1H NMR (500 MHz, C6D6): 1.17 (tert-BuO, 9H, s), 1.29 (MeSi, 3H, s), 1.41(CH2, 4H, m), 1.49 (CH2, 2H, m), 1.64 (CH2, 2H, m), 1.89 (CH2, 4H, m),1.94 (CH2, 2H, m), 3.30 (tert-BuO-CH2, 2H, t), 6.81 (Flu-H, 2H, m), 6.90(Flu-H, 2H, m), 7.14 (Flu-H, 4H, m), 7.60 (Flu-H, 4H, d), 7.65 (Flu-H,2H, d), 7.78 (Flu-H, 2H, d)

Examples 1 to 13

Toluene was added to a 500 ml glass reactor and then 1-hexene (or1-octene for Example 2) was put into the reactor and a 10 wt % solutionof methyl aluminoxane (MAO) in toluene was added thereto. Then, a 1 mMsolution of the product prepared in Production Example 1,(tert-Bu-O—(CH₂)₆)MeSi(9-C₁₃H₉)₂ZrCl₂) in toluene was put into thereactor and then a polymerization reaction was initiated by introducingethylene into the reactor. After the resulting mixture was stirred for apredetermined time, the gas in the reactor was vented and a solution ofethanol and hydrochloric acid was poured into the reaction product,which was then stirred, filtered, and then washed with ethanol, and thensubjected to evaporation of the solvent to provide an olefin blockcopolymer.

Regarding the above examples, the content of 1-hexene (or 1-octene) inthe total amount of monomers including 1-hexene (or 1-octene) andethylene was varied to prepare olefin block copolymers.

Comparative Example 1

As an olefin elastomer, an ethylene-1-octene random copolymer marketedby LG. Chem. Ltd. under the trade name of LUCENE™ LC170 was used forComparative Example 1.

Comparative Example 2

As an olefin block copolymer, an ethylene-1-octene block copolymermarketed from Dow Chemical Co., Ltd. under the trade name of INFUSE™9107 (Melt Index (190° C., 2.16 kg): 1 g/10 min; Density: 0.866 g/cm³)was used for Comparative Example 2.

Some properties of the ethylene-α-olefin copolymers as obtained fromExamples 1 to 13 and the polymer of Comparative Examples 1 and 2 weremeasured in accordance with the methods set forth in the followingexperimental examples.

Experimental Examples (1) WAXD Pattern Analysis

With using a micro injection molding system (model name: Haake MinijetII, manufactured by Thermo Electron Co., Ltd.), the copolymers obtainedfrom the examples and the comparative examples were melted at 220° C.for three minutes, and then were subjected to a injection molding with arectangular bar type mold at 40° C. and maintained for 30 seconds. Then,the resulting product was subjected to aging at 250 bar for 60 secondsto provide a sample having a rectangular bar shape (64 mm*12.7 mm*3.2mm). Each of the samples was used for a density measurement and a WAXDanalysis.

For comparison, the WAXD patterns for the block copolymer of Example 8,the random copolymer of Comparative Example 1, and the block copolymerof Comparative Example 2 were shown together in FIG. 1. (In FIG. 1, thesolid line: Example 8, the alternating long and short dashed line:Comparative Example 1, and the dashed line: Comparative Example 2) Inaddition, likewise, the WAXD analysis was carried out for each ofExamples 1 to 7 and Examples 9 to 13 to derive the WAXD pattern. In thisregard, the drawing range for the WAXD pattern was limited to the 2θrange from about 11° to about 35°.

From the WAXD patterns derived as above, deconvolution was conductedwith a single line fitting by using a Fundamental parameter (FP)approach of Bruker TOPAS program to obtain the area of each peak and theratio therebetween. In this regard, the TOPAS program was run with usingthe Chebychev 3^(rd) order function. In addition, for the first and thesecond peaks shown at 2θ of 21.5±0.5° and about 23.7±0.5°, the center ofeach peak in the TOPAS program was designated at 2θ of about 20 to 22°and about 22 to 24°, respectively, and then the deconvolution wasconducted with a single line fitting to obtain the area of each peak.Each peak area was put into the formula, (the area of the first peak at21.5±0.5°)/(the area of the second peak at 23.7±0.5°), to calculate thepeak area ratio. The specific 2θ values and the peak area ratios foreach peak that are derived as above are summarized in Table 1.

For the first peak of the WAXD pattern, the FWHM value was alsodetermined by using the area function of the Bruker EVA program. In thisregard, with the measured range of the first peak as designated from 20°to 23°, it was measured by using the area function. The FWHM values thusobtained are summarized in Table 1.

In the analysis of the WAXD pattern, the measuring instruments beingused were as follows:

Measuring Instruments:

Bruker AXS D8 Endeavor XRD

Cu Kα radiation (wave length; 1.5418 Å)

Vantek position sensitive detector (PSD window: 6°)

Goniometer radius: 217.5 mm

Full Axial model-primary/secondary soller: 2.3°

(2) Degree of Crystallization

First, the area of each peak was calculated in accordance with themethod as set forth in section (1). In the WAXD pattern derived as setforth in section (1), the measurement range was also set to be the 2θrange of about 11° to 35°. The center of the halo (the amorphous regionpattern that was shown in the lower part of the crystalline peak)appearing in the measurement range was designated as an approximate 2θvalue near the center of the above measurement range, and deconvolutionwas conducted with a single line fitting to provide the halo area. Thedegree of crystallization was obtained by putting the values of eachpeak area and the halo area into Mathematical Formula 2. The results aresummarized in Table 1. In the WAXD pattern, the drawing range for themeasurement of the degree of crystallization was limited to the 2θ rangefrom about 11° to 35°. The measuring instruments were the same as setforth in section (1).

Degree of Crystallization(%)={(B+C)/(A+B+C)}*100  [Mathematical Formula2]

In Mathematical Formula 2, A represents the area of the WAXD patterncorresponding to the amorphous region in the 2θ range from about 11° to35°, for example the halo area as shown in the 2θ range from about 11°to 35°, and B represents the peak area shown at about 21.5±0.5°, and Crepresents the peak area shown at about 23.7±0.5°.

(3) Density

The density was measured in a Mettler balance by using the sample of therectangular bar (64 mm*12.7 mm*3.2 mm) that was obtained for the WAXDanalysis in section (1). The obtained results are summarized in Table 1.

(4) Melting temperature (T_(m)) and Crystallization temperature (T_(c))

The copolymer sample was heated from a temperature of 30° C. to atemperature of 200° C. at a heating rate of 20° C./min with itsequilibration state being maintained, and was kept at that temperaturefor five minutes, and thereby thermal history of the sample waseliminated. Again, the sample was cooled to 10° C. at a rate of 10°C./min to find out the exothermic peak corresponding to thecrystallization temperature. After being kept at 10° C. for one minute,the sample was heated up to 200° C. at a heating rate of 10° C./min, andthen kept at that temperature for one minute and cooled again to 30° C.,and then the experiment was completed.

In the measurement results obtained from DSC (Differential Scanningcalorimeter, manufacture by TA instruments, DSC2920 model), the top ofthe heat flow curve depending on the temperature within the rangedescending at a rate of 10° C./min was determined as the crystallizationtemperature. Within the range ascending at a rate of 10° C./min, thepeak having a larger area was determined as a first peak and the peakhaving a smaller area as a second peak. In this regard, the heating andthe cooling rates were 10° C./min, respectively. The results measured inthe second heating range was used for determining the meltingtemperature. The melting temperature and the degree of crystallizationas measured are summarized in Table 2.

(5) Analysis of the DSC Pattern

After the DSC pattern was derived in the same manner as set forth insection (4), and the first peak and, if present, the second peak weredetermined, and then with the base line for each peak determinedtherefrom, each peak area over the base line was calculated. In thisregard, for each peak, the highest point of the heat flow curve (in thecase where the second derivative of the curve in the DSC pattern isbelow zero) or the lowest point of the heat flow curve (in the casewhere the second derivative of the curve in the DSC pattern is abovezero) was set as the top of each peak, and the base line was determinedbased on the top of the peak. The base line was set as the lineconnecting two highest points of the heat flow curve in the range ofabout ±20° C. based on the top of the peak wherein the second derivativeof the curve in the DSC pattern is below zero. By contrast, the baseline was set as the line connecting two lowest points of the heat curvein the above range of the peak wherein the second derivative is abovezero. The value of Mathematical Formula 1 was calculated from the areasof the first and the second peaks, and it was also checked whether thesecond peak was present. The value of Mathematical Formula 1 and thepresence of the second peak were checked for Examples 1 to 13 andComparative Example 1, respectively. The results are summarized in Table2.

A2/(A1+A2)  Mathematical Formula 1

In Mathematical Formula 1, A1 and A2 represent the areas of the firstand the second peaks, respectively.

(6) Analysis for the Hard Segment Content

For the copolymers of the examples and the comparative examples, thecontent (mole fraction) of the hard segment was calculated by usingcommercialized Time-Domain NMR equipment (TD NMR equipment manufacturedby Bruker Optics Co., Ltd., tradew name: Minspec). First, the FreeInduction Decay (FID) for the samples of the examples and thecomparative examples were measured by using such TD NMR equipment. TheFID thus measured was expressed as a function of the time and theintensity. In addition, a function having a graph most similar to thatof the FID function was derived with varying four constants of A, B,T2_(fast), and T2_(slow), and then A, B, T2_(fast), and T2_(slow) foreach sample were determined therefrom.

It has been known in the art that in the case of the hard segment, T2(spin-spin relaxation time) relaxation derived therefrom appears to bevery fast, while T2 (spin-spin relaxation time) relaxation derived fromthe soft segment appears to be very slow. Therefore, among the values ofA, B, T2_(fast), and T2_(slow) being determined in the above, a lowervalue of T2 was determined as the T2 value of the hard segment (i.e.,T2_(fast)), and a higher value of T2 was determined as T2 value of thesoft segment, (i.e., T2_(slow)). From these results, the content (mol %)of the hard segment was calculated together with the constants, A and B.The hard segment was calculated in the same manner as previouslymentioned for Examples 2, 3, 7, 12, 13, and Comparative Examples 1 and 2are summarized in Table 1.

Intensity=A×EXP(−Time/T2_(fast))+B×EXP(−Time/T2_(slow))  [MathematicalFormula 3]

The values of A, B, T2_(fast), T2_(slow) were determined throughfitting, respectively.

Hard segment(mol %)=A/(A+B)×100

In Mathematical Formula 3, the intensity and the time are the valuesderived from the results of the FID analysis, T2_(fast) is the T2(spin-spin relaxation time) relaxation value for the hard segment, andT2_(slow) is the T2 (spin-spin relaxation time) relaxation value for thesoft segment. Further, A and B are the constants determined by thefitting and have the value proportionate to the content of each segment,representing the relative ratios of the hard segment and the softsegment, respectively.

(7) Molecular weight and Molecular Weight Distribution (PolyDispersityIndex: PDI)

A number average molecular weight (M_(n)) and a weight average molecularweight (M_(w)) were measured by using gel permeation chromatography(GPC), and then the value of the molecular weight distribution wascalculated by dividing the weight average molecular weight by the numberaverage molecular weight. The weight average molecular weight and thePDI for the molecular weight distribution are summarized in Table 2. Thecharacteristic values calculated according to the aforementioned methodsare compiled in Table 1 and Table 2, respectively.

(8) Analysis for the Content of the α-Olefin Repeating Units

For the copolymers of the examples 1 to 13, the comparative examples 1and 2, the contents (mole fraction) of the 1-hexene or 1-octenerepeating units were measured by using 1H-NMR spectroscopy.Specifically, the contents are measured by quantifying methyl peak atabout 0.9 ppm in the 1H-NMR spectrum.

TABLE 1 The content The ratio between of 1-hexene The first peak Thesecond peak the areas of the Degree of Content of the (or 1-octene) inWAXD pattern in WAXD pattern first peak and the crystallization Densityhard segment Sample (mol %) 2θ(°) FWHM 2θ(°) second peak (%) (g/cm³)(mol %) Example 1  6.6 21.4 0.514 23.6 2.3 23 0.898 No measured valueExample 2  9.9 21.5 0.505 23.7 2.4 23 0.886 50.8 (Oc) Example 3 10.621.5 0.509 23.7 2.3 22 0.885 47.5 Example 4 11.4 21.3 0.522 23.7 2.6 210.883 No measured value Example 5 11.8 21.4 0.511 23.7 2.2 22 0.880 Nomeasured value Example 6 11.8 21.5 0.498 23.7 2.5 19 0.876 No measuredvalue Example 7 12.7 21.5 0.489 23.8 2.2 20 0.876 39.9 Example 8 12.521.4 0.505 23.7 2.1 19 0.875 No measured value Example 9 13.0 21.4 0.51023.7 2.5 20 0.875 No measured value Example 10 12.9 21.5 0.510 23.7 2.318 0.873 No measured value Example 11 14.1 21.5 0.503 23.7 2.4 18 0.869No measured value Example 12 15.0 21.4 0.517 23.7 2.7 16 0.868 30.9Example 13 17.9 21.5 0.498 23.7 2.3 16 0.865 26.6 Comp. Example 1 12.0No No No — — 0.873 — (Oc) peak peak peak Comp. Example 2 16.3 21.5 0.34123.8 4.5 20 0.866 30.8 (Oc) * “Oc” refers to using 1-octene for theα-olefin monomer instead of 1-hexene. * For Examples 1, 4 to 6, and 8 to11, there was no measured result for the content of the hard segment. *The polymer of Comparative Example 1 was a random copolymer so that itwas impossible to define a plurality of blocks or segments, and thus noresult was obatined for the content of the hard segment.

TABLE 2 DSC Pattern analysis Value Presence of the Poly- of the formulaTm Tc dispersity second A2/ Samples (° C.) (° C.) Mw index peak (A1 +A2) Example 1 121 107.2 119200 2.89 no 0.00 Example 2 118 103.5 1380003.10 no 0.00 Example 3 120 104.3 129400 2.98 no 0.00 Example 4 122 105.4107700 2.87 yes 0.15 Example 5 122 105.3 101500 2.73 yes 0.12 Example 6121 104.6 96400 2.52 no 0.00 Example 7 120 105.0 99800 3.20 yes 0.22Example 8 122 104.0 102600 2.60 yes 0.23 Example 9 120 105.2 102200 2.74yes 0.08 Example 10 120 104.9 96800 2.70 yes 0.08 Example 11 121 106.596700 2.82 yes 0.29 Example 12 119 105.1 98200 2.68 yes 0.37 Example 13118 104.3 75200 3.20 no 0.00 Comparative 56 59.0 99700 2.49 no 0.00Example 1 Comparative 124 91.0 73000 2.62 No measured value Example 2 *For Comparative Example 2, there was no measured result for the DSCpattern analysis.

With reference to Table 1 and FIG. 1, the block copolymer of theexamples were found to have crystalline characteristics wherein in theWAXD pattern the peaks were shown at the 2θ of about 21.5±0.5° and about23.7±0.5° and the ratio between the peak areas defined by (the peak areaat about 21.5±0.5°)/(the peak area at about 23.7±0.5°) was no more than3.0. It was also found that the FWHM value of the peak shown at about21.5±0.5° was at least about 0.45° and the degree of crystallization wasfrom about 10 to 30%. With regard to the DSC pattern, the blockcopolymer of the examples were also observed to have the first peak at amelting temperature, and optionally the second peak at anothertemperature, satisfying that the ratio between the areas of the firstand the second peaks was at least zero but less than one.

In contrast, the random copolymer of Comparative Example 1 was adifferent type of copolymer from the block copolymers of the examplessuch that it was impossible to define a plurality of blocks or segments.Besides, it showed no peak in the WAXD pattern and thus failed to haveany of the aforementioned crystalline characteristics. The blockcopolymer of Comparative Example 2 was also found to have differentcharacteristics from the block copolymer of the examples because itsFWHM value and the peak area ratio were different therefrom.

It was found that the block copolymers of the examples with such novelcrystalline characteristics exhibited excellent heat resistance as wellas a high melting point that is much higher than that of ComparativeExample 1 and comparable to that of Comparative Example 2. In addition,the block copolymer of the examples were found to have a highercrystallization temperature and a broadened molecular weightdistribution when being compared with the copolymer of ComparativeExamples 1 and 2. From these results, it was confirmed that the blockcopolymers of the examples had a higher speed of the crystallizationwhen being subject to a melting process in comparison with thecopolymers of Comparative Examples 1 and 2, indicating excellentprocessability and moldability into a product.

In addition, the block copolymers of the examples have the hard segmentsand the soft segments defined therein and they comprise each segment ina certain content, and they have a certain amount of the α-olefinmonomers copolymerized therein to show a certain degree of density,exhibiting excellent elasticity as an elastomer.

1-7. (canceled)
 18. A method of producing an olefin block copolymer,comprising: subjecting ethylene or propylene and an α-olefin tocopolymerization at a temperature of 70 to 150° C. in the presence of acatalyst composition comprising a metallocene catalyst having a Group IVtransition metal and a Lewis base functional group, and a cocatalysthaving a Lewis acid element and an organic functional group; wherein atthe copolymerization temperature, there occur alternatively between themetallocene catalyst and the cocatalyst a first state in which the Lewisbase functional group and the Lewis acid element form an acid-base bondand a second state in which the metallocene catalyst and the cocatalysthas no interaction therebetween; and wherein the Group IV transitionmetal of the metallocene catalyst and the organic functional group ofthe cocatalyst do interaction with each other in the first state. 19.The method of producing an olefin block copolymer in accordance withclaim 18, wherein the α-olefin is at least one selected from the groupconsisting of 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene,1-heptene, 1-octene, 1-decene, 1-undecene, 1-do decene, 1-tetradecene,1-hexadecene, and 1-itocene.
 20. The method of producing an olefin blockcopolymer in accordance with claim 18, wherein the metallocene catalystcomprises a metallocene compound of Chemical Formula 1:

in Chemical Formula 1, R1 to R17 are the same with or different fromeach other, and are independently hydrogen, a halogen, a C₁-C₂₀ alkylgroup, a C₂-C₂₀ alkenyl group, a C₆-C₂₀ aryl group, a C₇-C₂₀ alkylarylgroup, or a C₇-C₂₀ arylalkyl group, respectively, L is a straight orbranched chain C₁-C₁₀ alkylene group, D is —O—, —S— or —N(R)—, wherein Ris hydrogen, a halogen, a C₁-C₂₀ alkyl group, a C₂-C₂₀ alkenyl group, ora C₆-C₂₀ aryl group, A is hydrogen, a halogen, a C₁-C₂₀ alkyl group, aC₂-C₂₀ alkenyl group, a C₆-C₂₀ aryl group, a C₇-C₂₀ alkylaryl group, aC₇-C₂₀ arylalkyl group, a C₂-C₂₀ alkoxy alkyl group, a C₂-C₂₀heterocyclic alkyl group, or a C₅-C₂₀ heteroaryl group, and when the Dis —N(R)—, R can be linked with A to form a heterocycle comprisingnitrogen, for example, a five to eight membered heterocycle such aspiperidinyl or pyrrolydinyl moiety, M is a Group IV transition metal, X1and X2 are the same with or different from each other, and areindependently a halogen, a C₁-C₂₀ alkyl group, a C₂-C₂₀ alkenyl group, aC₆-C₂₀ aryl group, a nitro group, an amido group, a C₁-C₂₀ alkylsilylgroup, a C₁-C₂₀ alkoxy group, or a C₀-C₂₀ sulfonate group, respectively.21. The method of producing an olefin block copolymer in accordance withclaim 18, wherein the cocatalyst comprises a compound of ChemicalFormula 3:—[Al(R18)-O]_(n)—  [Chemical Formula 3] in Chemical Formula 3, R18s arethe same with or different from each other, and are independently aC1-C20 hydrocarbon; or a C1-C20 hydrocarbon substituted with a halogen;and n is an integer of at least two.